Fluorescent agents



Patented Mar. 18, 1952 UNITED STATES PATENT OFFICE FLUORESCENT AGENTSPaul E. -Hoch and William H. Libby, Easton, Pa.,

assignors to General Aniline & Film Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application January 15, 1951, SerialNo. 206,126

This invention relates to novel fluorescent-compounds of thediamidostilbenedisulfonic acid series.

It has been found that novel fluorescent compounds of thediamidostilbenedisulfonic acid series which are characterized by thefollowing general formula are particularly valuable for the whitening orbrightening of textiles by incorporating a minor amount thereof in soapsor detergents used ior washingtextiles. These novel compounds have theformula A OR where R is a haloalkyl or haloalkenyl group selected fromthe group consisting of CH2CH2X, CH2CH2CH2X,

and

wherein X is Clor Br; and M represents a member of the group consistingof H and a cation usually alkali metal or alkaline earth metal.

These compounds are readily prepared by condensing one molecularproportion of 4,4'-diamino- 2,2'-stilbenedisulfonic acid with a slightexcess of about two molecular proportions of a haloalkoxy orhaloalkenoxy benzoyl halide.

The preparation of the novel compounds of the present invention is fullydescribed in the following specific examples.

Example 1 To 9.25 parts of 4,4'-diamino-2,2'-stilbenedisulfonic aciddissolved in 30 parts of water and 38 parts of a 20 percent aqueoussodium carbonate solution there is added 51 parts of acetone and theresulting mixture cooled to -5" C. A solution of 16.4 parts ofZ-(fi-chloroethoxy)-benzoyl chloride in 20 parts of acetone is addeddropwise. The temperature is held at 0-5 C. during the ad- 7 Claims.(01. 260-507) dition and the reaction mixture is maintained alkaline toBrilliant Yellow throughout by the addition of small portions of asodium carbonate solution. When the reaction is complete, the mixture isallowed to warm to room temperature and the product isolated in theusual manner.'

The product corresponds to the formula:

O3Na 0-"CH2-CH2C1 2 When this material is incorporated into dischargepastes and applied to fabrics, the whites thus obtained are remarkablywhiter than those obtained using ordinary discharge pastes. When thismaterial is applied to fibers of cellulose,

wool or nylon, by methods well known in the art, the white appearance ofthe fabric is thereby much improved.

If small amounts of this substance are added scribed in copendingapplication of Hoch et al.,

Serial No. 209,918, filed January I, 1951 by the reaction of ethyleneoxide on methyl salicylate and the reaction product then converted tothe acid chloride with thionyl chloride. During this last reaction thehydroxyl group of 2-( 3-hydroxyethoxy) -benzoic acid is also replaced bychlorine.

Example 2 The procedure described in the first paragraph of Example 1was repeated, using in place of the 2- (fl-chloroethoxy) -benzoylchloride, 16.l parts of 3-(5-chloroethoxy) benzoyl chloride. The productobtained had the following-formula:

OaNa OHgCHzCl 2 a 3 and was substantially similar in properties to theproduct of Example 1.

The 3-(- 8-chloroethoxy)-benzoyl chloride employed in this example wasobtained in the manner similar to that described in the last paragraphof Example 1 using 3-hydroxy methylbenzoate in place ofmethylsalicylate.

Example 3 The procedure of paragraph 1 of Example 1 was repeated, using16.4 parts of l-(p-chloroethoxy)-benzoy1 chloride in place of the2-(pchloroethoxy) benzoyl chloride. A product having the followingformula was obtained:

OaNa O V =CH-QNH-JLL OSNa angers-mm 2 1 TheQ-ly-chIorOpropOXy) -benzoylchloride used in this example was prepared in a manner similar to thatoutlined in the last paragraph of Example 1 using trimethylene oxide inplace of ethylene oxide.

Example 5 The synthesis of paragraph 1 of Example 1 was repeated using17 .4 parts of 2-( 8-chlorobutoxy)- benzoyl chloride in place of2-(fl-chloroethoxy)- benzoyl chloride. A product similar in propertiesto that of Example 1 and having the following formula was obtained:

The 2 -(fl-chlorobutoxy) -benzoyl chloride employed in this example wasprepared in a manner similar to that outlined in the last paragraph ofExample 1 using butylene oxide-1,2 instead of ethylene oxide. 7

r 7 Example 6 The synthesis of paragraph 1 of Examplel was repeatedusing in place of the 2- (p-chloroethoxy) benzoyl chloride 17.4 parts ofZ-(fi-chloropropene- 2-oxy) -benzoyl chloride. A product having proprideused in this example was prepared by reacting chloro allyl chloride(2,3-dichloropropene) with methyl salicylate in the presence of an acidacceptor. The resulting ester was converted to the acid chloride byhydrolysis and the action of thionyl chloride.

It will be apparent that, if desired, the free acids corresponding tothe sodium salts obtained in the specific examples may readily beproduced by acidifying the sodium salt with a strong mineral acid. Theseproducts are normally employed in the form of their sodium salt.However, for special applications other salts may be desired.

The potassium salt may readily be obtained by neutralization of the freeacid with potassium hydroxide or may be obtained directly by usingpotassium carbonate in place of sodium carbonate neutralization of freeacids.

erties similar to that of Example 1 andof the following formula wasobtained:

- soaNa )CH COI=CHz 2 The 2-(fl-chloropropene-2-oxy) -benzoyl chloin'the above examples.

' A salt such as barium or strontium salts, which have been found to beof interest for the whitening of photographic prints, may be obtained byWhere spirit solubility is desired, the various amine salts, such ascyclohexylamine salts, may be desired and may be obtained byneutralization of the free acids.

We claim: 1. Fluorescent agents of the formula W NHl OzH wherein Rrepresents a member of the group consisting. of haloalkyland'haloalkenyl radicals of the formula of chlorine and bromine; andsalts thereof.

2. Fluorescent agents of the formula and salts thereof. 7

3. Fluorescent agents of the formula S OaH CHzOHzCl 2 and salts thereof.

4. Fluorescent agents of the formula 0 gin -O 03H (BCHzCHzCl 2 and saltsthereof.

5. Fluorescent agents of the formula 0 =OH NEH) SOaH CHr-CHz-CHzCl 2 andsalts thereof.

6. Fluorescent agents of the formula,

and salts thereof.

bCHzCHCk-CHzCHs 2 7. Fluorescent agents of the formula.

and salts thereof.

PAUL E. HOCH. WILLIAM H. LIBBY.

REFERENCES CITED Name Date Eberhart et a1 Apr. 26, 1949 Number

1. FLUORESCENT AGENTS OF THE FORMULA